Polymeric composition containing fatty acid derivative or morpholine



United States Patent POLYMERIC COMPOSITION CONTAINING FATTY ACID DERIVATIVE OR MORPHOLINE Harold P. Dupuy, Leo A. Goldblatt, and Frank C. Magne, New Orleans, La., assignors to the United States of America'as represented by the Secretary of Agriculture No Drawing. Filed Jan. 13, 1959, Ser. No. 786,661 12 Claims. ((31.106-176) (Granted under Title35, US. Code (1952), sec. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to nitrogen-containing derivatives of ricinoleic acid. More'particularly, this invention relates to the morpholides and cyanoethylated derivatives of ricinoleic acid and its derivatives. These nitrogencontaining compounds have utility as plasticizers for both vinyl chloride polymers and for cellulose esters.

Ricinoleic acid is a unique fatty acid found in castor oil in the form of an ester of glycerol. Ricinoleic acid normally comprises about 90% of the fatty acids present, as glycerides, in castor oil. Chemically, ricinoleic acid is l2-hydroxyoleic acid or 12-hydroxy-9-octadecenoic acid which may be represented by the following formula:

A morphohde of an acid is an amide of the acid in which the amide nitrogen atom is a nitrogen atom of a morpholine ring. Prior workers have produced the morpholides and other amides of some of the more common fatty acids. Themorpholides have generally been prepared by the reaction of morpholine with acid chlorides, acids, or acid anhydrides.

Cyanoethylated derivatives are conventionally produced by vinyl addition of acrylonitrile (CH =CHCN) to reactive hydrogen atoms contained in alcohols, phenols, and the like compounds. Each reactive hydrogen atom causes a vinyl group of the acrylonitrile to become saturated, thus producing cyanoethylated derivatives having beta-substituted propionitrile groups attached via ether linkages. The cyanoethylation reaction has been applied in the prior art to a large number of monohydric and polyhydric alcohols, as Well as to numerous other compounds having reactive hydrogen atoms.

A primary object of the present invention is to provide processes for producing new morpholides and cyanoethylated derivatives of ricinoleic acid and its derivatives. A further object is to produce novel nitrogen-containing plasticizers from ricinoleic acid and its derivatives, said plasticizers being suitable for plasticizing either vinyl chloride polymers or cellulose esters. Other objects will be apparent from the description of the invention.

In general, according to this invention, the esters of ricinoleic acid and of its derivatives are reacted with morpholine to produce the morpholides. It is generally preferred to use the methyl esters for this ammonolysis reaction, although other esters such as ethyl esters, propyl esters etc. may also be employed. When the preferred methyl esters are subjected to the ammonolysis reaction with morpholine, the hydrogen atom of the secondary amine structure of the morpholine combines with the ICC the morpholide, according to the following equation:

where R represents an alkyl or alkenyl group having an alcoholic hydroxyl substituent. The hydroxyl group can either be left free and unreacted, or it can be made to react with any of the reactants commonly used for reacting with alcoholic hydroxyl groups.

Suitable methyl ester reactants include: methyl ricinoleate; methyl lZ-hydroxystearate; methyl ricinelaidate; and the like. Suitable reactants for introducing substituents on the hydroxyl groups ofthe morpholides include acetic anhydride for making acetoxy derivatives, acrylonitrile for making cyanoethylated derivatives, and the like reagents commonly used for reacting with alcoholic hydroxyl groups.

The reaction for preparation of morpholides according to this invention proceeds smoothly at relatively moderate temperatures in the absence of a catalyst. The morpholides can be obtained in substantially quantitative yield simply by refluxing the methyl esters with morpholine, while at the same time distilling off the methyl alcohol as it is formed in the reaction. This is the preferred procedure. Since the distillation temperature of methyl alcohol is quite low as compared to that of morpholine, efiicient fractionation is not required and relativelylittle of the morpholine distills over with the methanol during the course of the reaction. The progress of the reaction can be followed conveniently by observing the rise in reflux temperature or more accurately by titrating aliquots of the reaction mixture to ascertain the quantity of unreacted morpholine remaining.

It is generally preferred to carry out the reaction at a temperature at least as high as the reflux temperature of the particular mixture of reactants being employed. Temperatures considerably lower than this are not generally suitable, since the rate of reaction becomes too slow to be practical. Extremely high temperatures are not desirable, especially when unsaturated methylester reactants are used, since there is danger of degradation, modification, or decomposition of-the reactants.

While the morpholine and the ester reactants combine in a 1:1 ratio, it is usually preferred to employ an excess of morpholine. About 2 moles of morpholine for each mole of ester is particularly suitable.

The length of reaction time can be controlled depending on the particular reactants being employed and the extent of conversion desired by the operator. Essentially complete conversion to the morpholide is usually achieved in about 36 hours under the preferred conditions.

Although suitable unreactive solvents for the reactants can be used in the reaction mixture, it is not generally desirable or advantageous to employ such solvents. The morpholine and ester reactants are mutually soluble and provide a homogeneous reaction mixture without the incorporation of a solvent.

The isolation and recovery of the morpholide product can be accomplished without difficulty. At the end of the reaction period, the excess morpholine is removed, preferably by distillation at a pressure below normal atmospheric pressure. The morpholide product remaining can be used without further purification, or it can be purified by conventional means. Distillation, solvent crystallization, and the like are generally preferred means for purifying the morpholides.

' employed for acylations.

The unreacted hydroxyl group of the morpholide prodnets of the present invention can be acrylated with the usual acylating agents under the conditions conventionally For example, unique acetoxy 4 is an economical and effective polymerization inhibitor. When using water, we prefer to use about 0.1 part by weight of inhibitor for each part by weight of reactant being cyanoethylated.

derivatives can be prepared by treating said morpholides 5 W le temperatures ranging from about room temwith acetic anhydride. It is generally preferred to use perature to the decomposition temperature of the rean excess of acetic anhydride and heat the reaction mixactants n b used, maximum p ra res f fr m ture to a temperature below the decomposition temperaab0ut'70 C. to about 85 C.'are particularly suitable ture of the reactants during the acylation. It is confor employment in the cyanoethylation process of the venient to employ about 1 part by weight of the a eti present invention. A preferred procedure is to add the anhydride for each part by Weight of morpholide, and acrylonitrile to the reaction mixture at such a rate that to carry out the acylation reaction at the reflux temas the reaction proceeds the temperature of the mixture perature of the reaction mixture until the desired extent gradually rises to the'p'referred maximum reaction temof reaction is obtained. The acetoxy derivative is readily Perature (about tO Following isolated by means of distillation or other conventional plete addition of the acrylonitrile, the reaction mixture procedures, is maintained 'at the said preferred maximum reaction In preparing cyanoethylated derivatives of n'cinoleic temperature a sufiicient length of time until the desired acid derivatives according to the process of the present extent of cyanoethylation is achieved. From about 50% invention, acrylonitrile is reacted with the reactive hyto about 80% conversion to cyanoethylated product is drogen atoms of the alcoholic hydroxyl groups of the achieved in about 3 to 4 hours under the preferred rericinoleic acid derivatives. The cyanoethylated products action conditions. The cyanoethylated product can be contain beta-substituted propionitrile groups attached by isolated and recovered without difliculty by employing means of ether linkages. For example, when 4-ricinoconventional procedures such as phasic separations, disleoylmorpholine is the reactant being cyanoethylated the tillations, crystallization from solvents and the like. reaction can be represented by the following equation: The nitrogen-containing derivatives of the present inoH2oHt o H O N-C-(CHz)1rCH=OHCHiJ(CH2)5-CHa+GHFCHCN- cHrCz H CHr-CHz O 1?. O NC (CH2)r-CH=CHCHz-?(CH)5-CHa CHr-CHs o lHzoHzCN Suitable reactants which can be cyanoethylated invention have unique plasticizing properties. They exclude: 4-ricinoleoylmorpholine; 4-(12-hydroxystearoyl)- hibit good compatibility with polymers and copolymers morpholine;ricinoley1 alcohol; and the like. When ricinof monomers predominating in Vi y chloride, Such as oleyl alcohol is used as the reactant, both of the alco- 40 polyvinyl chloride, and the vinyl chloride-vinyl acetate holic hydroxyl groups of said reactant are cyanoethylated copolymers predominating in vinyl chloride. They can to yield the di-cyanoethoxy compound, namely, 1,12-dibe employed as plasticizers in proportions of from about beta-cyanoethoxy-9-octadecene. 10 to 80 parts by weight per 100 parts by weight of The cyanoethylation reaction proceeds readily at modpolymer. In addition, some of the nitrogen-containing erate temperatures in the presence of an alkaline eataderivatives are likewise suitable as plasticizers for celylst. Any of the conventional alkaline catalysts, such lulose esters, such as cellulose acetate. They can usually as metallic sodium or potassium (producing the correbe employed in proportions of up to about 40 parts by sponding alkoxides) may be used. We prefer to employ weight per 100 parts by weight of cellulose acetate and a quaternary amine base type catalyst, such as benzylstill exhibit good compatibility. The suitability of the trimethylammonium hydroxide and the like. The connitrogen containing derivatives of ths inventon as plascentratiorr f catalyst in th ti n mi t re c n be ticizers for two such widely different types of materials varied widely. About 0.04 part by weight of quateris unique. nary amine for 1 part by weight of reactant being cyano- The following examples are given by way of illusethylated is particularly suitable. tration and not by way of limitation of the invention;

It is generally preferred to conduct the reaction in a Example 1 suitable solvent medium. Any solvent in which the reactants are soluble and which is unreactive toward the A mlXthYe of 312 grams H1016) of methyl fl reactants is generally suitable. Dioxane is a particu- 16316 and 174 grams moles) of mol'pholihe Was heated larly uitable solvent The of olvent employed 111 a reaction flask under gentle reflux for about can bervaried widely but about 1 Part by weight f hours. The methyl alcohol produced during the course Solvent f r each part by weight f reactant being cyano- 69 of the reaction was allowed to distill out of the reaction ethylated i usually r f d flask through a short Vigreaux column and condensed in The relative amounts of ricinoleic acid derivative and a Dean'stafk P- During the 36 hour reaction period, acrylonitrile in the reaction mixture can be varied widely. the reaction temperature gradually I056 from to However, since these two reactants combine in a 1:1 and approximately 1 H1015 0f fhfithy1 31601101 ratio for each hydroxyl group undergoing cyanoethylawas evolved- At the f of the reaction P the tion, it is desirable to assure at least this theoretical ratio the Dreaded molphohhe was removed y distillation i the reaction mixture. An excess f acrylonitrile i under vacuum. The reaction product was distilled, yieldusually preferred. About 2 moles of acrylonitrile for ihg 230 grams of matel'iai distilling at at each mole of hydroxyl group in the reactant being cyanomillimeters; D 25 in hyl i particularly i b1 70 The purified product contained 71.47% carbon, 11.02%

The use of a polymerization inhibitor in the reaction y h i hitmgeh, and hydroxyl, as

'mixture is desirable' Otherwise, an excessive amount termlhed y Conventional analytical procedures- The of the 'acrylonitrile will polymerize to form polyacryloni- Product Was thus Shown 6 4-ficiholeoyimol'phohhe trile and thus be unavailable for the cyanoethylation re- Which has theoretical content of Carbon, action. Water is preferred, in view of the fact thatit 75 11.24% hydrogen, 3.81% nitrogen and 4.63% hydroxyl.

The compatibility of the plasticizers with the vinyl chloride polymers in all of the examples was determined on the basis that exudation or bleeding out of the plasticizer within 15 days was poor, and a lack of bleeding for at least 45 days was good.

The 4-ricinoleoylmorpholine was also tested as a plasticizer for cellulose acetate. Thirty parts by weight of plasticizer and 100 parts by weight of cellulose acetate (40% acetyl content) were dissolved in acetone, and cast films were prepared from the acetone solution by allowing the solvent to evaporate slowly from portions of the solution placed in shallow dishes. The films were stripped from the dishes, heated 1 hour at 80" C., and examined. The films were dry and clear, indicating compatibility of the plasticizer with the cellulose acetate.

Example 2 One part by weight of the 4-ricinoleoylmorpholine of Example 1 was refluxed with 1 part by weight of acetic anhydride for about 2 hours. The acetic acid and excess acetic anhydride were then removed from the reaction mixture by distillation under vacuum. The acetoxy derivative was purified by distillation at 0.2 millimeters pressure, its distillation temperature being 230234 C. at this pressure. The purified product had the following characteristics: N 1.4789; d 0.9836; 20.35. It was found to contain 69.99% carbon, 10.53% hydrogen, 3.24% nitrogen and hydroxyl. The product was thus shown to be 4-(12-acetoxyoleoyl)morpholine which has a theoretical content of 70.37% carbon, 10.58% hydrogen, 3.24% nitrogen, and 0% hydroxyl.

The 4-(12-acetoxyoleoyl)morpholine was compared with DOP in the standard formulation described in Example 1. The results are given in Table 11.

TABLE II Compati- Tensile 100% Elonga Brittle bility strength, modulus. tion, point,

p.s.i. p.s.i. percent C.

4-(12-acetoxy- Good 2, 990 1, 370 840 -23 oleoyDmorpholine. DOP Go0cl 3,000 1,650 320 -31 The 4-(l2-acetoxyoleoyl)morpholine was tested as a plasticizer for cellulose acetate (40% acetyl) as described in Example 1. Good compatibility was obtained using either thirty or forty parts by weight of plasticizer per 100 parts by Weight of cellulose acetate.

Example 3 6 bon, 11.79% hydrogen, 3.75% nitrogen, and 4.59% hydroxyl. The product was thus shown to be 4-(12-hydroxystearoyl)morpholine which has a theoretical content of 71.49% carbon. 11.73% hydrogen, 3.79% nitrogen, and 4.60% hydroxyl.

Example 4 One part by weight of the 4-(12-hydroxystearoyl) morpholine of Example 3 was refluxed with 1 part by weight of acetic anhydride for about 2 hours. The acetic acid and excess acetic anhydride were then removed by vacuum distillation. The reaction product was purified by distillation at 0.2 millimeters pressure, its distillation temperature being 234-235 C. at this pressure. The purified product had the following characteristics: N 1.4709; d 0.9726. It was found to contain 69.62% carbon, 11.17% hydrogen, 3.24% nitrogen, and 0% hydroxyl. The product was thus shown to be 4-(12- acetoxystearoyl)morpholine which has a theoretical content of 70.03% carbon, 11.02% hydrogen, 3.40% nitrogen, and 0% hydroxyl.

The 4-(12-acetoxystearoyl)morpholine was compared with DOP in the standard formulation described in Example 1. The results are given in Table HI.

TABLE III Oomoati- Tensile 100% Elonga- Brittle bility strength, modulus, tion. point,

p.s.i. p.s.i. percent C.

4-(12-ac/etoxy- Good 2, 980 1,510 300 -21 stearoyDmorpholiue. DOP G00d 3,000 1,650 320 -31 ExampleS Example 6 368 grams (1 mole) of the 4-ricinoleoylmorpholine of Example 1 was dissolved in 368 grams of dioxane. To this solution was added 37 milliliters of water as a polymerization inhibitor and 37 milliliters of Triton B (a 40% by weight solution of benzyltrimethylammonium hydroxide in methyl alcohol) as catalyst. Two moles (106 grams) of acrylonitrile was then added dropwise to the mixture with stirring during a 30-minute period, during which time the temperature rose to about C. The reaction mixture was stirred and maintained at about 75 C. for three additional hours, and was poured While still warm into 3 liters of diethyl ether. The solution was allowed to stand a few hours to precipitate most of the polyacrylonitrile. The ethereal solution was decanted from the precipitate, filtered, and the filtrate was neutralized with dilute aqueous hydrochloric acid and then I washed free of excess acid with water. The resulting ethereal layer was vacuum distilled to remove ether, and then distilled rapidly under high vacuum to isolate the cyanoethylated product. The fraction which distilled at 248254 C. at 20 microns pressure was purified by crystallization from 15 volumes of methyl alcohol at -70 C. overnight. The purified product had the following characteristics: N 1.4816; c cm, 14.20. It was found to contain 70.74% carbon, 10.40% hydrogen, and 6.64% nitrogen. The product was thus shown to be 7 4-(12-beta-cyanoethoxyoleoyl)morpholine which has a theoretical content of 71.38% carbon, 10.54% hydrogen, and 6.66% nitrogen.

The 4-(1Z-beta-cyanoethoxyoledyl)morpholine was compared with DOP in the standard formulation described in Example 1. The results are given in Table IV.

TABLE IV Compati- Tensile 100% Elonga- Brittle bility strength, modulus, tion, point,

p.s.i. p.s.i. percent 0.

4-(12-beta-eyano- Goot1 3,000 1,550 340 25 ethoxyoleoyD- morpholine. DO]? God. 3,000 1.560 350 -33 Example 7 370 grams (1 mole) of the 4-(12-hydroxystearoyl)- morpholine of Example 3 was cyanoethylated with 106 grams (2 moles) of acrylonitrile in the same manner and under the same conditions as described in Example 6. In this case, the acrylonitrile was added during a 20-minute period and the temperature of the reaction mixture rose to about 80 C. The mixture was then stirred and maintained at 70 C. for three additional hours. The reaction mixture was further processed as described in Example 6. The fraction of the reaction product which distilled at 246-252 C. at 25 microns pressure was purified by crystallization from volumes of acetone at -25 C. overnight to precipitate non-cyanoethylated morpholide. Acetone was removed from the resulting filtrate by vacuum distillation to obtain the cya'noethylated morpholide. It was recrystallized from volumes of methyl alcohol at -70 C. overnight. The recrystallized product contained 70.85% carbon, 10.85% hydrogen, and 6.55% nitrogen. The product was thus shown to be 4-(12-beta-cyanoethoxystearoyl)morpholine which has a theoretical content of 71.04% carbon, 10.97% hydrogen, and 6.63% nitrogen.

The 4-(1Z-beta-cyanoethoxystearoyl)morpholine was compared with DOP in the standard formulation described in Example 1. The compatibility of the 4-(12- beta-cyanoethoxystearoyl)morpholine was good. Its percent elongation was 380% as compared to 320% for DOP, and its tensile strength was 3120 p.s.i. as compared to 3000 p.s.i. for DOP.

7 Example 8 1284 grams (1 mole) of ricinoleyl alcohol was dissolved in 284 grams of dioxane. To this solution was added 28 milliliters of water as a polymerization inhibitor and 28 milliliters of Triton B (a 40% by weight solution of benzyltrimethylammom'um hydroxide in methyl alcohol) as catalyst. Four moles (212 grams) of acrylonitrile was then added dropwise to the mixture with stirring during a 1-hour period, during which time the temperature rose to about 70 C. The reaction mixture was stirred and maintained at about 70 C. for three additional hours, and was poured while still warm into 3 liters of diethyl ether. The solution was allowed to stand a few hours to precipitate most of the polyacrylonitn'le. The ethereal solution was decanted from the precipitate and the ether was removed from the solution by vacuum distillation. The residue was distilled rapidly under high vacuum. The fraction which distilled at 228238 C. at 25 microns pressure was crystallized from 15 volumes of methanol at 70 C. overnight. The purified product had the following characteristics: N 1.4632; 14.30. It was found to contain 74.20% carbon, 11.18% hydrogen, and 7.08% nitrogen. The product was thus shown to be 1,12-di-beta-cyano- 8 ethoxy-9-octadecene which has a theoretical content of 73.79% carbon, 10.84% hydrogen, and 7.17% nitrogen. The 1,12-dirbeta-cyanoethoxy-9-octadecene was com pared with DOP in the standard formulation described in Example 1. The results are given in Table V.

TABLE V Gompati- Tensile 100% Elonga- Brittle bility strength, modulus, tion, point,

p.s.i. p.s.i. percent C.

1,12-di-beta-cyano- Good. 2,840 1,210 350 55 etboxy-9 -octadecene. DOP (30011---- 3,030 1,520 370 37 We claim:

1. A plastic composition which is stable against exudation of plasticizer comprising a mixture containing a polymer selected from the group consisting of cellulose acetate, polyvinylchloride and a vinyl chloride-vinyl acetate copolymer which contains a predominant amount of vinyl chloride, and a plasticizer therefor comprising selected from the group consisting of 1,12-di-[3-cyanoethoxy-9-octadecene, 4-ricinoleoylmorpholine, 4 (l2 hydroxystearoyl)morpholine 4-ricinelaidoylmorpholine, 4- (12-acetoxyoleoyl)morpholine, 4-(12 acetoxystearoyl)- morpholine, 4-(12 beta-cyanoethoxyoleoyl)morpholine, and 4-( 12 beta cyanoethoxystearoyl)morpholine, said plasticizer being present in the proportion of about from 10 to parts per parts of the vinyl chloride polymer.

2. The plastic composition of claim 1 wherein the plasticizer is 4-ricinoleoylmorpholine.

4. The plastic composition of claim 1 wherein the plasticizer is 4-ricinelaidoylmorpholine.

5. The plastic composition of claim 1 wherein plasticizer is 4-(l2-acetoxyoleoyl)morpholine.

6. The plastic composition of claim 1 wherein plasticizer is 4-(l2-acetoxystearoyl) morpholine:

7. The plastic composition of claim 1 wherein the plasticizer is 4-(12-beta-cyanoethoxyoleoyl)morpholine.

8. The plastic composition of claim 1 wherein the plasticizer is 4-(12-beta-cyanoethoxystearoyl)morpholine.

9. A plastic composition which is stable against exudation of plasticizer comprising a mixture of polyvinyl chloride and a plastizer therefor comprising from about 10 to 80 parts of 1,1Z-di-beta-cyanoethoxy-9-octadecene per 100 parts of polyvinyl chloride.

10. A plastic composition which is stable against exudation of plasticizer comprising a mixture of a vinyl chloride-vinyl acetate copolymer which contains a predominant amount of vinyl chloride and a plasticizer therefor comprising from about 10 to 80 parts of 1,12- di-fi-cyanoethoxy-9-octadecene per 100 parts of copolymer.

11. A film-forming composition of matter comprising cellulose acetate as its essential film-forming ingredient, and a plasticizer therefor comprising 4-ricinoleoylmorpholine.

12. A fihn-forming composition of matter comprising cellulose acetate as its essential film-forming ingredient and a plasticizer therefor comprising 4-(12-acetoxyoleoyl)morpholine.

the

the

References Cited in the file of this patent UNITED STATES PATENTS 2,393,802 Morey et al. Jan. 29, 1946 2,638,471 Burger May 12, 1953 2,649,445 Specter Aug. 18, 1953 2,758,104 Adelman Aug. 7, 1956 

1. A PLASTIC COMPOSITION WHICH IS STABLE AGAINST EXUDATION OF PLASTICIZER COMPOSITION A MIXTURE CONTAINING A POLYMER SELECTED FROM THE GROUP CONSISTING OF CELLULOSE ACETATE, POLYVINYLCHLORIDE AND A VINYL CHLORIDE-VINYL ACETATE COPOLYMER WHICH CONTAINS A PREDOMINANT AMOUNT OF VINYL CHLORIDE, AND A PLASTICIZER THEREFOR COMPRISING SE LECTED FROM THE GROUP CONSISTING OF 1,12-DI-B-CYANOETHOXY-9-OCTADECENE, 4-RICINIOLEOYLMORPHOLINE, 4-(12-HYDROXYSTEAROYL)MORPHOLINE, 4-RICINELAIDOYLMORPHOLINE, 4(12-ACETOXYOLEOYL)MORPHOLINE 4-(12 - ACETOXYSTEAROYL)MORPHOLINE, 4-(12-BETA-CYANOETHOXYOLEOYL)MORPHOLINE, AND 4-(12-BETA - CYANOETHOXYSTEAROYL)MORPHINE, SAID PLASTICIZER BEING PRESENT IN THE PROPORTION OF ABOUT FROM 10 TO 80 PARTS PER 100 PARTS OF THE VINYL CHLORIDE POLYMER. 